CN108383315B - Multistage electrically driven ionic membrane's waste water recovery device - Google Patents
Multistage electrically driven ionic membrane's waste water recovery device Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 169
- 239000002351 wastewater Substances 0.000 title claims abstract description 58
- 238000011084 recovery Methods 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 204
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 90
- 239000011780 sodium chloride Substances 0.000 claims abstract description 69
- 150000003839 salts Chemical class 0.000 claims abstract description 40
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 52
- 238000001914 filtration Methods 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 39
- 150000002500 ions Chemical class 0.000 claims description 25
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 23
- 150000001450 anions Chemical class 0.000 claims description 20
- 150000001768 cations Chemical class 0.000 claims description 19
- 238000002425 crystallisation Methods 0.000 claims description 17
- 230000005712 crystallization Effects 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 16
- 239000010802 sludge Substances 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 9
- 238000005189 flocculation Methods 0.000 claims description 8
- 230000016615 flocculation Effects 0.000 claims description 8
- 238000001471 micro-filtration Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- 239000004575 stone Substances 0.000 claims description 6
- 229910001385 heavy metal Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- -1 silicon ions Chemical class 0.000 claims description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001424 calcium ion Inorganic materials 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000004065 wastewater treatment Methods 0.000 claims description 2
- 230000003750 conditioning Effects 0.000 claims 1
- 239000000706 filtrate Substances 0.000 claims 1
- 239000012141 concentrate Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000010865 sewage Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 239000003729 cation exchange resin Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000002035 prolonged Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000001187 sodium carbonate Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 240000000218 Cannabis sativa Species 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000015450 Tilia cordata Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229940077747 antacids containing calcium compounds Drugs 0.000 description 1
- 229940077744 antacids containing magnesium compounds Drugs 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229940043430 calcium compounds Drugs 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000005039 chemical industry Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001112 coagulant Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 235000012765 hemp Nutrition 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 235000012766 marijuana Nutrition 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 238000009285 membrane fouling Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003204 osmotic Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000001376 precipitating Effects 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water, or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/041—Treatment of water, waste water, or sewage by heating by distillation or evaporation by means of vapour compression
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Abstract
The invention provides a wastewater recovery device of a multistage electrically driven ionic membrane, which is based on a medium-pressure reverse osmosis device and a high-pressure reverse osmosis device to carry out preliminary reduction treatment to obtain medium concentrated water, the secondary electric driven membrane device and the tertiary electric driven membrane device are used for deeply concentrating the moderately concentrated water to obtain high-concentrated water, and the moderately concentrated water is obtained by jointly processing the moderately concentrated water through the medium-pressure reverse osmosis device and the high-pressure reverse osmosis device. The present invention has high water and salt recovering rate and low cost.
Description
The invention is a divisional application of a method for treating high-salt wastewater by using a multistage electrically driven ionic membrane, wherein the application number is 201510980910.5, the application date is 2015, 12 and 23, and the application type is invention.
Technical Field
The invention relates to the field of sewage recovery equipment, in particular to a wastewater recovery device with a multistage electrically driven ionic membrane.
Background
In recent years, in the rapid development of industries such as petrochemical industry, electric power industry, metallurgy industry, coal chemical industry and the like, the amount of sewage with complex components, such as reverse osmosis concentrated water, industrial sewage, circulating sewage, partial process drainage and the like generated in the industrial production process, is increased year by year, and how to finally dispose and utilize the sewage with complex components is widely regarded.
The reverse osmosis technology is used for treating wastewater at present, the development is relatively fast, but a large amount of wastewater after the reverse osmosis treatment cannot be effectively utilized, and the cost for recovering salts contained in the wastewater through evaporative crystallization is too high. In addition, the reverse osmosis membrane element is easily polluted by organic matters, and the saturated inorganic salt calcium and magnesium compounds are easy to scale on the membrane surface, so that the service life of the reverse osmosis membrane element is influenced, and the filtering effect is reduced.
Chinese patent CN104355431A discloses an apparatus for efficiently treating and recovering reverse osmosis concentrated water and high salt-containing wastewater. After the equipment is primarily filtered by two stages of vibrating membranes, the obtained fresh water is deeply filtered and purified by a reverse osmosis membrane, and the concentrated water obtained by filtering by the vibrating membranes is evaporated, crystallized and recycled. The treatment process is shortened without measures such as softening and removing oil of the waste water, but the recovery efficiency of the salts and the fresh water is low. And the water content in the concentrated water is still higher after the concentration treatment by the two-stage vibrating membranes, and the cost for recovering salt by evaporation crystallization is too high.
Patent publication No. CN103319042A (reference 1) discloses an integrated apparatus and process for recycling and zero-discharging high-salinity complex wastewater, which specifically discloses a wastewater pretreatment process for performing sedimentation or flocculation treatment, a wastewater concentration treatment process for performing reverse osmosis filtration by using medium-pressure membrane elements and ultrahigh-pressure membrane elements, and a treatment process for crystallizing and recovering concentrated brine. Compared with the invention, the technical means of separation treatment by adopting the primary, secondary and tertiary electrically driven ionic membranes and the specific parameters of the pressure difference between the concentrated water chamber and the dilute water chamber are not limited. It cannot achieve the technical effect of high recovery rate of the salts of the present invention.
Patent publication No. CN103508602A (reference 2) discloses a process for discharging high salinity industrial wastewater integrated with membrane and evaporative crystallization, which specifically discloses a technical means of filtering insoluble solid impurities in water by ultrafiltration pretreatment, concentrating the permeate obtained by ultrafiltration pretreatment by an impermeable membrane filtration device and an electrodialysis device, and finally obtaining salty mud and salts by evaporative crystallization. Compared with the invention, the technical means of grading wastewater treatment by matching a two-stage reverse osmosis device with a three-stage electrically-driven ionic membrane is lacked, and the technical effect of greatly improving the recovery efficiency of fresh water by the invention cannot be obtained.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a method for treating high-salt-content wastewater by using a multi-stage electrically-driven ionic membrane, which is characterized in that the method is used for carrying out reverse osmosis filtration and electrically-driven ionic membrane separation treatment on the high-salt-content wastewater after pretreatment, so as to efficiently recover desalted water.
Wherein the pretreatment process removes heavy metal ions, hardness ions and organic substances in the high-salt-content wastewater through precipitation and/or flocculation adsorption and adjusts the pH value to obtain the pretreated concentrated water.
And in the reverse osmosis filtration process, the pre-treated concentrated water is subjected to preliminary reduction treatment through medium-pressure reverse osmosis filtration and high-pressure reverse osmosis filtration to obtain medium concentrated water.
In the electrically-driven ionic membrane separation process, the moderate concentrated water is deeply concentrated through a first-stage electrically-driven membrane treatment program, a second-stage electrically-driven membrane treatment program and a third-stage electrically-driven membrane treatment program so as to obtain high concentrated water in a reduced amount, thereby facilitating the recovery of salts through evaporation crystallization.
The first-stage electrically driven membrane treatment process adopts a monovalent cation selection membrane and a monovalent anion selection membrane so as to separate monovalent cations and monovalent anions in the moderately concentrated water, moderately concentrated water of salts formed by the monovalent cations and the monovalent anions is obtained in a concentrated water chamber, and the separated moderately concentrated water mainly containing high-valence cations and/or high-valence anions is obtained in a fresh water chamber.
The concentrated water containing high-valence cations and/or high-valence anions is further concentrated by a secondary electrically-driven membrane treatment process to obtain high-concentration water of high-valence salts for evaporation crystallization recovery,
the salt concentrated water formed by the univalent cations and the univalent anions is further concentrated by a three-level electrically driven membrane treatment procedure to obtain high concentrated water of low-valence salt for evaporation crystallization recovery,
wherein the pressure of the concentrated water chamber in the second-level electrically driven membrane treatment procedure and the pressure of the concentrated water chamber in the third-level electrically driven membrane treatment procedure are both 0.1-0.4MPa higher than the pressure of the fresh water chamber.
According to a preferred embodiment, the monovalent cation is sodium, the monovalent anion is chloride and the higher anion is sulfate. The low-valence salt is sodium chloride, and the high-valence salt is sulfate. Preferably the higher salt is sodium sulphate.
The first-stage electrically driven membrane treatment process adopts a monovalent cation selective membrane and a monovalent anion selective membrane to separate and obtain sodium chloride concentrated water and concentrated water mainly containing sulfate.
And the concentrated water mainly containing sulfate enters a secondary electric driven membrane treatment procedure, and is further concentrated to obtain high concentrated water of sulfate, so that evaporation, crystallization and recovery are directly carried out.
And the sodium chloride concentrated water enters a three-level electrically driven membrane treatment procedure, and is further concentrated to obtain high concentrated water of sodium chloride, so that evaporation, crystallization and recovery are directly carried out.
Wherein the pressure of the concentrated water chamber in the second-level electrically driven membrane treatment program and the pressure of the concentrated water chamber in the third-level electrically driven membrane treatment program are both 0.2-0.35MPa higher than the pressure of the fresh water chamber.
The scale-formed hardness ions, heavy metal ions and organic matters which easily pollute the membrane are removed through pretreatment, so that the service life of the membrane in the reverse osmosis filtering device is greatly prolonged, the burden of subsequent reverse osmosis filtration and electric drive membrane separation is reduced, the filtration and separation efficiency is increased, and the recovery rate of fresh water is improved.
Sodium chloride and sulfate are separated by a selective electrically driven ionic membrane, and then are directly evaporated and crystallized after being deeply concentrated and reduced by the electrically driven membrane to obtain the sodium chloride and the sulfate.
Through reverse osmosis treatment and multi-stage reduction treatment of an electrically driven ionic membrane, the salt content in the concentrated water is greatly increased, so that the burden of recovering salts through evaporative crystallization is relieved, and fresh water is recovered more fully.
According to a preferred embodiment, the primary electrically driven membrane unit employs a Neosepta CMS monovalent cation selective membrane and a Neosepta ACS monovalent anion selective membrane.
According to a preferred embodiment, the pressure of the concentrated water chamber of the secondary electrically-driven membrane device and the pressure of the concentrated water chamber of the tertiary electrically-driven membrane device are both higher than the pressure of the fresh water chamber.
According to a preferred embodiment, the pressure difference between the concentrated water chamber and the fresh water chamber of the secondary electrically-driven membrane device is 0.25MPa-0.35MPa, the pressure difference between the concentrated water chamber and the fresh water chamber of the tertiary electrically-driven membrane device is 0.2MPa-0.3MPa,
according to a preferred embodiment, the TDS value of the concentrate after the pretreatment process is 0.1 × 104mg/L～1×104mg/L, the TDS value of the moderate concentrated water is 1 × 10 after the reverse osmosis filtration process4mg/L～6×104mg/L, the TDS value of the high concentration water is 1 × 10 after the electrically driven ion membrane separation process5mg/L～3×105mg/L。
According to a preferred embodiment, the TDS value of the concentrate after the pretreatment process is 0.5 × 104mg/L～1×104mg/L, the TDS value of the moderate concentrated water is 5 × 10 after the reverse osmosis filtration process4mg/L～6×104mg/L, the TDS value of the high concentration water is 1.2 × 10 after the electrically driven ion membrane separation process5mg/L～2×105mg/L。
According to a preferred embodiment, the TDS values of the sodium chloride concentrate and the sulfate concentrate are each about 1 × 10 after treatment with the primary electrically driven membrane5mg/L, the TDS values of the sodium chloride high-concentration water and the sulfate high-concentration water are both about 2 × 10 after the two-stage electrically driven membrane treatment and the three-stage electrically driven membrane treatment5mg/L。
Most water has been retrieved through the reverse osmosis process, makes the high waste water that contains salt obtain the concentration, handles the back through two-stage electric drive membrane again, further retrieves fresh water and makes the waste water degree of depth concentrated, through minimizing the processing to the water yield that needs the evaporation when the crystallization recovery salt that has significantly reduced, the energy saving consumes, and has improved the rate of recovery of water and salt.
According to a preferred embodiment, the fresh water chambers of the secondary electrically-driven membrane device and the tertiary electrically-driven membrane device are provided with hard porous membrane supporting elements so as to homogenize the liquid flow, the liquid can be mixed when passing through the porous membrane supporting elements, the liquid flow path is increased, the residence time of the liquid is prolonged, and the separation is more complete. The membrane supporting element provides supporting force for the electrically driven membrane, so that the pressure on the membrane is more uniform, the osmotic pressure of the concentrated water chamber is balanced, and the electrically driven membrane is prevented from being damaged under the pressure.
According to a preferred embodiment, the membrane support element is porous stone and/or porous plastic. Preferably, the membrane support member is filled in the fresh water chamber.
According to a preferred embodiment, the effective porosity of the membrane support element surface is greater than 50%.
According to a preferred embodiment, the membrane support element is a porous fabric secured by a rigid frame. The porous fabric is fixed in the fresh water chamber and is close to or attached to the electrically driven membrane.
According to a preferred embodiment, the porous fabric is a fabric made of glass fibers and/or hemp fibers.
According to a preferred embodiment, the pores of the membrane support element are interconnected irregular pores.
According to a preferred embodiment, the fresh water obtained in the electrically driven ion membrane separation process is again subjected to a reverse osmosis filtration process to further separate fresh water and salts. The inlet water of the electrically driven ionic membrane separation process is medium concentrated water with high salt content, the salt content of the separated fresh water is also slightly high, and the recovery rate of the salts is increased by carrying out reverse osmosis treatment on the fresh water again.
According to a preferred embodiment, the medium-pressure reverse osmosis filtration process uses a medium-pressure reverse osmosis device with a flow channel width of 50mil to 70mil, and the high-pressure reverse osmosis filtration process uses a high-pressure reverse osmosis device with a flow channel width of 70mil to 90 mil.
According to a preferred embodiment, the medium-pressure reverse osmosis filtration process uses a medium-pressure reverse osmosis device with a flow channel width of 65mil, and the high-pressure reverse osmosis filtration process uses a high-pressure reverse osmosis device with a flow channel width of 80 mil. The reverse osmosis filter element is not easy to generate scale formation or organic matter pollution blockage through the design of the large flow passage.
According to a preferred embodiment, the pretreatment process comprises a preliminary sludge discharge by adding a pretreatment agent for sedimentation and/or flocculation adsorption, and a sludge discharge again by a microfiltration device to obtain the concentrate.
According to a preferred embodiment, the pretreatment process includes pretreatment agent treatment, microfiltration treatment, and resin hardening treatment to generate concentrated water. The resin removes hardness ions from the saturated wastewater to prevent scaling on the membrane during reverse osmosis. Preferably, the microfiltration treatment adopts a tubular microfiltration device or a submerged microfiltration device. Preferably the resin is a cation exchange resin.
According to a preferred embodiment, the pretreatment process removes organic matter, silicon ions, magnesium ions and/or calcium ions by precipitation and/or flocculation adsorption and adjusts the pH of the concentrate to be alkaline to prevent membrane fouling and scaling in the reverse osmosis process.
According to a preferred embodiment, the pre-treatment agent comprises one or more of lime, sodium hydroxide, sodium carbonate, polyaluminium chloride and polyacrylamide flocculant.
According to a preferred embodiment, the pretreatment process comprises adding sodium hydroxide, sodium carbonate, polyaluminium chloride and polyacrylamide flocculant in sequence, generating precipitate and adjusting the pH of the wastewater through the reaction of the sodium hydroxide and sodium carbonate with heavy metal ions and hardness ions, coagulating and adsorbing the precipitate and organic substances through the polyaluminium chloride and polyacrylamide flocculant, and precipitating the precipitate as sludge under the action of gravity. The sludge is precipitated at the bottom of the pretreatment device and discharged, and the supernatant enters the tubular microfiltration device for further filtration, so that the residual precipitate in the wastewater is removed, and adverse effects on a subsequent reverse osmosis filtration device and an electrically driven ionic membrane separation device are prevented.
According to a preferred embodiment, the pre-treated concentrate has a pH of 7.5 to 10.0.
According to a preferred embodiment, the PH of the pre-treatment concentrate is 8.0 to 9.5, and preferably the PH of the pre-treatment concentrate is 8.5 to 9.0. The alkaline condition can inhibit the tendency of silicon scaling and organic contamination on the surface of the reverse osmosis membrane.
According to a preferred embodiment, the moderately concentrated water is subjected to a de-hardening treatment by a resin, preferably a cation exchange resin, before entering the electrically driven ion membrane separation process.
According to a preferred embodiment, the sludge is dewatered by pressure filtration to form a dry sludge, and the water removed is treated again in a pretreatment process.
According to a preferred embodiment, the wastewater is passed through a cartridge filter before entering the medium-pressure reverse osmosis filtration unit, the high-pressure reverse osmosis filtration unit, the primary electrically driven membrane unit and/or the secondary electrically driven membrane unit, so as to prevent impurities from adversely affecting the units.
According to a preferred embodiment, the reverse osmosis membrane of the medium-pressure reverse osmosis filtration unit and/or the high-pressure reverse osmosis filtration unit is made of an aromatic polyamide composite material.
According to a preferred embodiment, the operating pressure of the medium-pressure reverse osmosis filtration device is between 1.5 and 4MPa and the operating pressure of the high-pressure reverse osmosis filtration device is between 3 and 5 MPa. The operation pressure of the preferred medium-pressure reverse osmosis filtering device is 2.0-3.5MPa, and the operation pressure of the high-pressure reverse osmosis filtering device is 3.5-4.5 MPa.
According to a preferred embodiment, the highly concentrated water is subjected to evaporative crystallization by a steam mechanical recompression technology to recover sodium sulfate and sodium chloride.
According to a preferred embodiment, the method comprises the steps of firstly carrying out flocculation precipitation by adding an alkaline pretreatment agent to remove partial organic matters, silicon ions, magnesium ions and/or calcium ions to obtain concentrated water, then carrying out reverse osmosis filtration by sequentially passing through a medium-pressure reverse osmosis device with a flow channel width of 65mil and a high-pressure reverse osmosis device with a flow channel width of 80mil, carrying out primary reduction treatment to recover fresh water, separating monovalent ions and high-valence ions from the medium-concentration water obtained by reverse osmosis by a primary electrically-driven membrane device to obtain concentrated water of sodium chloride in a concentrated water chamber and concentrated water mainly containing sulfate in a fresh water chamber respectively, wherein the primary electrically-driven membrane device adopts a Neosepta CMS monovalent cation selective membrane and a Neosepta ACS monovalent anion selective membrane, and the concentrated water mainly containing sulfate is further concentrated by a secondary electrically-driven membrane device to obtain high-concentration water of sulfate, the concentrated water chamber of the second-level electrically driven membrane device is higher than the pressure of the fresh water chamber by 0.3MPa, the concentrated water of the sodium chloride is further concentrated by a third-level electrically driven membrane device to obtain high concentrated water of the sodium chloride, the concentrated water chamber of the third-level electrically driven membrane device is higher than the pressure of the fresh water chamber by 0.2MPa, the fresh water chambers of the second-level electrically driven membrane device and the third-level electrically driven membrane device both contain porous stone and/or porous plastic as membrane supporting elements to prevent the electrically driven membrane from being damaged under the pressure, and the fresh water obtained in the electrically driven ionic membrane separation process is subjected to a reverse osmosis filtration process again to further separate fresh water and salts.
According to the method for treating the high-salt-content wastewater by using the multistage electrically-driven ionic membrane, provided by the invention, heavy metal ions, hardness ions, organic matters and the like in the high-salt-content wastewater are removed by pretreating the high-salt-content wastewater, so that adverse effects on a reverse osmosis device caused by scaling or membrane pollution and the like are prevented. Through the full-time cooperation of the two-stage reverse osmosis device and the three-stage electrically driven ionic membrane, wastewater is treated in a grading manner, the recovery efficiency of fresh water is greatly improved, meanwhile, the wastewater is subjected to reduction treatment through deep concentration, the evaporation burden during salt crystallization recovery is reduced, the method is simple, the recovery rate of fresh water and salt is high, and the cost is low.
Drawings
FIG. 1 is a process flow diagram of the invention for treating high salt-containing wastewater by using a multi-stage electrically driven ionic membrane; and
FIG. 2 is a schematic diagram of a system device for treating high-salt-content wastewater by using a multi-stage electrically-driven ionic membrane.
List of reference numerals
10: the pretreatment process 40: fresh water recovery process
11: homogenizing and homogenizing treatment 50: sludge treatment process
12: pretreatment agent treatment 60: process for recovery of salts
13: and (3) microfiltration treatment 61: recovery of sodium sulfate
14: primary softening treatment 62: sodium chloride recovery
20: preliminary reduction process 101: adjusting tank
21: medium-pressure reverse osmosis filtration 102: high density pond
22: high-pressure reverse osmosis filtration 103: tubular micro-filter
23: secondary softening treatment 104: first-stage resin tank
30: depth reduction process 201: medium-pressure reverse osmosis device
31: primary electrically driven membrane treatment 202: high-pressure reverse osmosis device
32: secondary electrically driven membrane treatment 203: two-stage resin tank
33: three-stage electrically driven membrane treatment 301: the primary electrically driven membrane device.
Claims (10)
1. A wastewater recovery device of a multistage electrically driven ionic membrane, which is characterized in that the wastewater recovery device comprises a medium-pressure reverse osmosis device, a high-pressure reverse osmosis device, a first-stage electrically driven membrane device, a second-stage electrically driven membrane device and a third-stage electrically driven membrane device, preliminary reduction treatment is carried out on the basis of the medium-pressure reverse osmosis device and the high-pressure reverse osmosis device to obtain medium concentrated water, and deep concentration is carried out on the medium concentrated water on the basis of the first-stage electrically driven membrane device, the second-stage electrically driven membrane device and the third-stage electrically driven membrane device to obtain high concentrated water, wherein,
the flow channel width adopted by the medium-pressure reverse osmosis device is 50-70 mil, the flow channel width adopted by the high-pressure reverse osmosis device is 70-90 mil, the medium-pressure reverse osmosis device and the high-pressure reverse osmosis device are jointly treated to obtain the medium-concentration water,
the first-stage electric driven membrane device adopts a Neosepta CMS monovalent cation selective membrane and a Neosepta ACS monovalent anion selective membrane to separate monovalent ions and high-valence ions in the medium-concentration water so as to respectively obtain concentrated water of sodium chloride in a concentrated water chamber and concentrated water mainly containing sulfate in a fresh water chamber,
the pressure of the concentrated water chamber of the secondary electrically-driven membrane device is 0.3MPa higher than that of the fresh water chamber and is used for further concentrating the concentrated water mainly containing sulfate to obtain high-concentration water of sulfate, the pressure of the concentrated water chamber of the tertiary electrically-driven membrane device is 0.2MPa higher than that of the fresh water chamber and is used for further concentrating the concentrated water of sodium chloride to obtain high-concentration water of sodium chloride, wherein,
the fresh water chambers of the two-stage electric driven membrane device and the three-stage electric driven membrane device both contain porous stones and/or porous plastics as membrane supporting elements to prevent the electric driven membranes from being damaged under pressure, and fresh water obtained by the treatment of the wastewater depth reduction process is returned to the primary wastewater reduction process for secondary filtration to further separate fresh water and salts, wherein,
the two-stage electrically driven membrane treatment (32) and the three-stage electrically driven membrane treatment (33) each separate a desalinated water which is about 85% of the total amount of the feed water, and the desalinated water is returned to the primary reduction process (20) for further treatment, wherein,
the desalted water returns to the medium-pressure reverse osmosis device (201) to be mixed with concentrated water for reverse osmosis filtration;
the desalinated water is returned to the high pressure reverse osmosis unit (202) for a second reverse osmosis filtration process.
2. The wastewater reclamation apparatus as recited in claim 1, further comprising a wastewater pretreatment apparatus, wherein,
the wastewater pretreatment device carries out precipitation and/or precipitation according to the addition of a pretreatment agentThe TDS value obtained by the mode of discharging the sludge again through the microfiltration device after the sludge is primarily discharged through flocculation adsorption is limited to 0.1 × 104mg/L~1×104Concentrated water in the range of mg/L,
the runner width that middling pressure reverse osmosis unit adopted is 50mil-70mil, the runner width that high pressure reverse osmosis unit adopted is 70mil-90mil, the warp middling pressure reverse osmosis unit and high pressure reverse osmosis unit are handled jointly and are obtained the TDS value and inject 1 × 104mg/L~6×104medium-concentration water in the range of mg/L,
the first-stage electric driven membrane device adopts a Neosepta CMS monovalent cation selective membrane and a Neosepta ACS monovalent anion selective membrane to separate monovalent ions and high-valence ions in the medium-concentration water so as to respectively obtain concentrated water of sodium chloride in a concentrated water chamber and concentrated water mainly containing sulfate in a fresh water chamber,
the pressure of the concentrated water chamber of the secondary electrically-driven membrane device is 0.3MPa higher than that of the fresh water chamber and is used for further concentrating the concentrated water mainly containing sulfate to obtain high-concentration water of sulfate, the pressure of the concentrated water chamber of the tertiary electrically-driven membrane device is 0.2MPa higher than that of the fresh water chamber and is used for further concentrating the concentrated water of sodium chloride to obtain high-concentration water of sodium chloride, wherein,
the fresh water chambers of the second-level electric driven membrane device and the third-level electric driven membrane device both contain porous stones and/or porous plastics as membrane supporting elements to prevent the electric driven membranes from being damaged under pressure, and fresh water obtained by the wastewater depth reduction process is returned to the primary wastewater reduction process, mixed with concentrated water treated by the wastewater pretreatment device and filtered again to further separate fresh water and salts.
3. The wastewater reclamation apparatus as recited in claim 2 wherein the dilute chambers of said secondary and tertiary electrically driven membrane devices have hard porous membrane support elements to homogenize the liquid flow and prevent damage to the electrically driven membranes under pressure.
4. The wastewater reclamation apparatus as recited in claim 2, wherein the wastewater pretreatment apparatus comprises a high-density tank and a tubular micro filter, wherein the wastewater pretreatment apparatus primarily discharges sludge by adding a pretreatment agent to the high-density tank for precipitation and/or flocculation adsorption and then discharges sludge again by a micro filter apparatus to obtain the concentrated water, and the wastewater treatment apparatus controls the pH of the concentrated water obtained by the treatment to be in the range of 7.5 to 10.0.
5. The wastewater reclamation apparatus as recited in claim 4, wherein the wastewater pretreatment apparatus further comprises a conditioning tank for performing a homogeneous uniform treatment of the wastewater and a primary resin tank for performing a primary softening treatment of the filtrate produced by the tubular microfilter.
6. The wastewater reclamation apparatus as recited in claim 5, further comprising a secondary resin tank for performing a secondary softening treatment on the moderately concentrated water treated by the high pressure reverse osmosis unit.
7. The wastewater reclamation apparatus as recited in claim 6, further comprising an intermediate reservoir for collecting and temporarily storing wastewater treated by a higher-stage apparatus and a booster pump for transferring wastewater in the intermediate reservoir to a lower-stage apparatus, which are disposed between the tubular micro filter and the primary resin tank, and between the primary resin tank and the medium-pressure reverse osmosis apparatus, and between the medium-pressure reverse osmosis apparatus, the high-pressure reverse osmosis apparatus, the secondary resin tank and the primary electrically driven membrane apparatus.
8. The wastewater reclamation apparatus as recited in claim 7, further comprising a sludge tank for collecting sludge, a reclamation water tank for collecting fresh water, and a salt reclamation apparatus, wherein,
the salt recovery device carries out evaporative crystallization on high-concentration water through a steam mechanical recompression technology to recover sodium sulfate and sodium chloride.
9. A method for treating high-salt wastewater by using a multistage electrically-driven ionic membrane is characterized in that an alkaline pretreatment agent is added to carry out flocculation precipitation to remove partial organic matters, silicon ions, magnesium ions and/or calcium ions to obtain concentrated water, then the concentrated water is subjected to reverse osmosis filtration by a medium-pressure reverse osmosis device with a flow channel width of 65mil and a high-pressure reverse osmosis device with a flow channel width of 80mil in sequence to recover fresh water, monovalent ions and high-valence ions of the medium-concentration water obtained by reverse osmosis are separated by a first-stage electrically-driven membrane device to obtain concentrated water of sodium chloride in a concentrated water chamber and concentrated water mainly containing sulfate in a fresh water chamber respectively, wherein the first-stage electrically-driven membrane device adopts a Neosepta CMS monovalent cation selective membrane and a Neosepta ACS monovalent anion selective membrane, the concentrated water mainly containing sulfate is further concentrated by a second-stage electrically-driven membrane device to obtain high-concentration water of sulfate, wherein the pressure of the concentrated water chamber of the second-level electrically driven membrane device is 0.3MPa higher than that of the fresh water chamber, the concentrated water of the sodium chloride is further concentrated by a third-level electrically driven membrane device to obtain high concentrated water of the sodium chloride, the pressure of the concentrated water chamber of the third-level electrically driven membrane device is 0.2MPa higher than that of the fresh water chamber, the fresh water chambers of the second-level electrically driven membrane device and the third-level electrically driven membrane device both contain porous stones and/or porous plastics as membrane supporting elements to prevent the electrically driven membrane from being damaged under pressure, the fresh water obtained in the electrically driven ionic membrane separation process returns to a reverse osmosis filtration process to be mixed with the pre-treated concentrated water and then is filtered again to further separate fresh water and salts, wherein,
the two-stage electrically driven membrane treatment (32) and the three-stage electrically driven membrane treatment (33) each separate a desalinated water which is about 85% of the total amount of the feed water, and the desalinated water is returned to the primary reduction process (20) for further treatment, wherein,
the desalted water returns to the medium-pressure reverse osmosis device (201) to be mixed with concentrated water for reverse osmosis filtration;
the desalinated water is returned to the high pressure reverse osmosis unit (202) for a second reverse osmosis filtration process.
10. The method for treating high-salinity wastewater by using the multi-stage electrically-driven ionic membrane according to claim 9, wherein the method is used for recovering desalted water with high efficiency by performing reverse osmosis filtration and electrically-driven ionic membrane separation treatment after the high-salinity wastewater is pretreated,
wherein, the method removes heavy metal ions, hardness ions and organic substances in the high-salinity wastewater through a wastewater pretreatment device and adjusts the pH value to obtain pretreated concentrated water,
carrying out preliminary reduction filtration treatment on the pretreated concentrated water through a medium-pressure reverse osmosis device and a high-pressure reverse osmosis device to obtain medium concentrated water,
the first-stage electric driven membrane device adopts a Neosepta CMS monovalent cation selective membrane and a Neosepta ACS monovalent anion selective membrane to separate monovalent ions and high-valence ions in the medium-concentration water so as to respectively obtain concentrated water of sodium chloride in a concentrated water chamber and concentrated water mainly containing sulfate in a fresh water chamber,
the medium concentrated water is deeply concentrated by a first-stage electrically driven membrane device, a second-stage electrically driven membrane device and a third-stage electrically driven membrane device to obtain high concentrated water so as to facilitate the evaporation, crystallization and salt recovery, wherein the medium concentrated water of salts formed by monovalent cations and monovalent anions and the medium concentrated water containing the high-valence cations and/or the high-valence anions are obtained by the separation of the first-stage electrically driven membrane device adopting a monovalent cation selection membrane and a monovalent anion selection membrane,
further concentrating the moderately concentrated water containing high-valence cations and/or high-valence anions by a two-stage electrically driven membrane device to obtain high-concentration water of high-valence salts so as to directly perform evaporative crystallization recovery,
further concentrating the moderately concentrated water of the salts formed by the monovalent cations and the monovalent anions through a three-stage electrically driven membrane device to obtain high concentrated water of low-valent salts so as to directly carry out evaporative crystallization recovery, wherein,
the pressure of the concentrated water chamber of the secondary electrically-driven membrane device is 0.3MPa higher than that of the fresh water chamber and is used for further concentrating the concentrated water mainly containing sulfate to obtain high-concentration water of sulfate, the pressure of the concentrated water chamber of the tertiary electrically-driven membrane device is 0.2MPa higher than that of the fresh water chamber and is used for further concentrating the concentrated water of sodium chloride to obtain high-concentration water of sodium chloride, wherein,
the fresh water chambers of the two-stage electric driven membrane device and the three-stage electric driven membrane device both contain porous stones and/or porous plastics as membrane supporting elements to prevent the electric driven membranes from being damaged under pressure, and fresh water obtained by the wastewater deep reduction process is returned to the primary wastewater reduction process for secondary filtration to further separate fresh water and salts.
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